The new polyarylenevinylene, structurally based on a terstyryl group linked by a maleimide group, was prepared from a new dibrominated diphenylmaleimide monomer and p-divinylbenzene by Heck-type Pd catalyzed polycondensation. The polymer was soluble in common organic solvents and had M-w and the polydispersity index of 73,600 g/mol and 5.0, respectively. Analysis with LR and NMR indicated that the polymer had a stereoregular vinylene sequence in the backbone of Z, E, E-configurations in series. The polymer showed optical absorption maximums at 353 nm and 444 nm and the bright orange red-colored photoluminescence at 570 nm in a solution and 590 nm in a film.